UV/visible light absorbers for ophthalmic lens materials

ABSTRACT

Benzotriazole UV/Visible light-absorbing monomers are disclosed. The UV/Vis absorbers are particularly suitable for use in intraocular lens materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 12/611,539, filedNov. 3, 2009, now U.S. Pat. No. 8,153,703, which claims priority under35 U.S.C. §119 to U.S. Provisional Patent Application No. 61/111,204,filed Nov. 4, 2008, the entire contents of which are incorporated hereinby reference.

FIELD OF THE INVENTION

This invention is directed to ultraviolet/visible light absorbers. Inparticular, this invention relates to novel benzotriazole monomersespecially suitable for use in implantable ophthalmic lens materials.

BACKGROUND OF THE INVENTION

Many ultraviolet and visible light absorbers are known as ingredientsfor polymeric materials used to make ophthalmic lenses. Such absorbersare preferably covalently bound to the polymeric network of the lensmaterial instead of simply physically entrapped in the material toprevent them from migrating, phase separating or leaching out of thelens material. Such stability is particularly important for implantableophthalmic lenses where the leaching of the absorber may present bothtoxicological issues and lead to the loss of UV/visible blockingactivity in the implant.

Numerous copolymerizable benzotriazole, benzophenone and triazineabsorbers are known. Most of these compounds are known as UV absorbers,though some may be known to also absorb some portion of visible light.Many absorbers contain conventional olefinic polymerizable groups, suchas methacrylate, acrylate, methacrylamide, acrylamide or styrene groups.Copolymerization with other ingredients in the lens materials, typicallywith a radical initiator, incorporates the absorbers into the resultingpolymer chain. Incorporation of additional functional groups on anabsorber may influence one or more of the absorber's light-absorbingproperties, solubility or reactivity. If the absorber does not havesufficient solubility in the remainder of the ophthalmic lens materialingredients or polymeric lens material, the absorber may coalesce intodomains that could interact with light and result in decreased opticalclarity of the lens.

Examples of polymeric ophthalmic lens materials that incorporate UVabsorbers can be found in U.S. Pat. Nos. 5,290,892; 5,331,073 and5,693,095.

SUMMARY OF THE INVENTION

The present invention provides benzotriazole light absorbing monomersthat absorb both ultraviolet light and a portion of visible light(“UV/Vis absorbers”). These absorbers are suitable for use in ophthalmiclenses, including contact lenses. They are particularly useful inimplantable lenses, such as intraocular lenses (IOLs).

The absorber compounds of the present invention absorb wavelengths oflight between 400-450 nm in addition to higher energy UVA rays between400-320 nm, UVB rays between 320-280 nm, and UVC rays below 280 nm. Theycontain reactive groups, which allow for covalent attachment of theabsorbers to ocular lens materials. Additionally, the absorbers of thepresent invention can be synthesized in approximately 5 steps fromreadily available starting materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows percent transmittance curves for UV/Vis absorber compoundsWL-1-WL-7.

FIGS. 2A-2J show percent transmittance curves for IOL materialscontaining UV/Vis absorber compounds WL-1-WL-4 that were subjected tophotostability testing producing the equivalent of 10 or 20 years oflight exposure.

DETAILED DESCRIPTION OF THE INVENTION

Unless indicated otherwise, all ingredient amounts expressed inpercentage terms are presented as % w/w.

The UV/Vis absorbers of the present invention are represented by theformula

wherein

R¹=H, CH₃, CH₂CH₃, or CH₂OH;

R²=C₁-C₄ alkyl or C₁-C₄ alkoxy; and

R³=H, CH₃, CH₃O, F, Cl, Br, I, or CF₃.

Preferred UV/Vis absorbers of the present invention are those whereinR¹=H or CH₃; R²=C₁-C₄ alkoxy; and R³=H, CH₃, CH₃O, F, Cl, or CF₃.

More preferred absorbers of the present invention are selected from thegroup consisting of:

-   2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl    methacrylate;-   3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl    methacrylate;-   3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl    methacrylate;-   3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl    methacrylate;-   2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl    methacrylate;-   2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl    methacrylate; and-   2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl    methacrylate.

Most preferred UV/Vis absorbers of the present invention are2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmeth acrylate and3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate.

The synthesis of the UV/Vis absorbers of the present invention isdescribed below.

Step 1: Phenol derivative 1 is synthesized via the hydroxymethylation ofp-methoxyphenol as shown below.

In steps 2 and 3, the diazonium salt of a 2-nitroaniline derivative issynthesized and subsequently reacted with 1 to form an azo dye.

In step 4, the azo dye is treated with a reducing agent, such asformamidinesulfinic acid, to form the corresponding benzotriazolecompound. The purity of the isolated benzotriazole compound can beenhanced by techniques known in the art, including filtration of excessreducing agent and reducing agent byproducts before addition of proticacids and column chromatography.

In step 5, the benzotriazole from step 4 is esterified to form a“reactive” compound which contains a vinyl group. By “reactive” it isunderstood that the vinyl group can polymerize to form covalent bondswhen reacted with vinyl monomers, co-monomers, macromers, crosslinkingagents, and other components typically used in making polymer-basedocular materials, particularly acrylics. The reactive groups arepreferably acrylate or methacrylate groups.

The UV/Vis absorbers of the present invention are particularly suitablefor use in IOLs. IOL materials will generally contain from 0.1 to 3%(w/w) of a UV/Vis absorber of the present invention. Preferably, IOLmaterials will contain from 0.2 to 2.5% (w/w) of an absorber of thepresent invention. Most preferably, IOL materials will contain from 0.3to 2% (w/w) of an absorber of the present invention. Such devicematerials are prepared by copolymerizing the absorbers of the presentinvention with other ingredients, such as device-forming materials,cross-linking agents, and optionally blue-light blocking chromophores.

Many device-forming monomers are known in the art and include bothacrylic and silicone-containing monomers among others. See, for example,U.S. Pat. Nos. 7,101,949; 7,067,602; 7,037,954; 6,872,793 6,852,793;6,846,897; 6,806,337; 6,528,602; and 5,693,095. In the case of IOLs, anyknown IOL device material is suitable for use in the compositions of thepresent invention. Preferably, the ophthalmic device materials comprisean acrylic or methacrylic device-forming monomer. More preferably, thedevice-forming monomers comprise a monomer of formula IV:

where in formula IV:

-   -   A is H, CH₃, CH₂CH₃, or CH₂OH;    -   B is (CH₂)_(m) or [O(CH₂)₂]_(z);    -   C is (CH₂)_(w);    -   m is 2-6;    -   z is 1-10;    -   Y is nothing, O, S, or NR′, provided that if Y is O, S, or NR′,        then B is (CH₂)_(m);    -   R′ is H, CH₃, C_(n′)H_(2n′+1) (n′=1-10), iso-OC₃H₇, C₆H₅, or        CH₂C₆H₅;    -   w is 0-6, provided that m+w≦8; and    -   D is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₆H₅, CH₂C₆H₅ or halogen.

Preferred monomers of formula IV are those wherein A is H or CH₃, B is(CH₂)_(m), m is 2-5, Y is nothing or O, w is 0-1, and D is H. Mostpreferred are 2-phenylethyl methacrylate; 4-phenylbutyl methacrylate;5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and3-benzyloxypropyl methacrylate; and their corresponding acrylates.

Monomers of formula IV are known and can be made by known methods. Forexample, the conjugate alcohol of the desired monomer can be combined ina reaction vessel with methyl methacrylate, tetrabutyl titanate(catalyst), and a polymerization inhibitor such as 4-benzyloxy phenol.The vessel can then be heated to facilitate the reaction and distill offthe reaction by-products to drive the reaction to completion.Alternative synthesis schemes involve adding methacrylic acid to theconjugate alcohol and catalyzing with a carbodiimide or mixing theconjugate alcohol with methacryloyl chloride and a base such as pyridineor triethylamine.

Device materials generally comprise a total of at least about 75%,preferably at least about 80%, of device-forming monomers.

In addition to an absorber of the present invention and a device-formingmonomer, the device materials of the present invention generallycomprise a cross-linking agent. The cross-linking agent used in thedevice materials of this invention may be any terminally ethylenicallyunsaturated compound having more than one unsaturated group. Suitablecross-linking agents include, for example: ethylene glycoldimethacrylate; diethylene glycol dimethacrylate; allyl methacrylate;1,3-propanediol dimethacrylate; 2,3-propanediol dimethacrylate;1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate;CH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ where p=1-50; andCH₂═C(CH₃)C(═O)O(CH₂)_(t)O—C(═O)C(CH₃)═CH₂ where t=3-20; and theircorresponding acrylates. A preferred cross-linking monomer isCH₂═C(CH₃)C(═O)O(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ where p is such that thenumber-average molecular weight is about 400, about 600, or about 1000.

Generally, the total amount of the cross-linking component is at least0.1% by weight and, depending on the identity and concentration of theremaining components and the desired physical properties, can range toabout 20% by weight. The preferred concentration range for thecross-linking component is 1-5% for small, hydrophobic compounds withmolecular weights typically less than 500 Daltons, and 5-17% (w/w) forlarger, hydrophilic compounds with molecular weights typically between500-5000 Daltons.

Suitable polymerization initiators for device materials containing aUV/Vis absorber of the present invention include thermal initiators andphotoinitiators. Preferred thermal initiators include peroxyfree-radical initiators, such as t-butyl (peroxy-2-ethyl)hexanoate anddi-(tert-butylcyclohexyl) peroxydicarbonate (commercially available asPerkadox® 16 from Akzo Chemicals Inc., Chicago, Ill.). Initiators aretypically present in an amount of about 5% (w/w) or less. Becausefree-radical initiators do not become chemically a part of the polymersformed, the total amount of initiator is customarily not included whendetermining the amounts of other ingredients.

The device materials containing a UV/Vis absorber of the presentinvention optionally also contain a reactive colorant. Suitable reactiveblue-light absorbing compounds include those described in U.S. Pat. No.5,470,932. Blue-light absorbers are typically present in an amount fromabout 0.01-0.5% (weight).

IOLs constructed of the materials of the present invention can be of anydesign capable of being rolled or folded into a small cross section thatcan fit through a relatively smaller incision. For example, the IOLs canbe of what is known as a one piece or multipiece design, and compriseoptic and haptic components. The optic is that portion which serves asthe lens. The haptics are attached to the optic and hold the optic inits proper place in the eye. The optic and haptic(s) can be of the sameor different material. A multipiece lens is so called because the opticand the haptic(s) are made separately and then the haptics are attachedto the optic. In a single piece lens, the optic and the haptics areformed out of one piece of material. Depending on the material, thehaptics are then cut, or lathed, out of the material to produce the IOL.

In addition to IOLs, the materials of the present invention are alsosuitable for use in other ophthalmic devices, such as contact lenses,keratoprostheses, and corneal inlays or rings.

The invention will be further illustrated by the following examples,which are intended to be illustrative, but not limiting.

Example 1 Synthesis of (2-hydroxy-5-methoxy-1,3-phenylene)-dimethanol

In a 2 liter reaction flask equipped with magnetic stirrer was suspended200 g p-methoxyphenol in 1300 ml water. Formaldehyde solution (335 ml,37% in water) was added to the stirring solution followed by 55.8 gcalcium oxide. The reaction mixture was covered in aluminum foil andallowed to stand at ambient temperature for 10 days. The solid wasfiltered and then suspended in 1 L deionized water. 130 ml glacialacetic acid was added to the stirring suspension at ambient temperature.The off-white solid was filtered, rinsed with hexane, and then driedunder high vacuum for 72 hours to afford 118.9 g (37.8%). ¹H NMR(DMF-d₇) delta: 3.75 (s, 3H, OCH₃), 4.73 (s, 4H, CH₂O), 5.39 (bs, 2H,CH₂OH), 6.85 (s, 2H, Ar—H). ¹³C NMR (DMF-d7) delta: 55.12 (1C, OCH₃),59.84 (2C, CH₂OH), 111.18 (2C, Ar—CH), 129.51 (2C, Ar—CCH₂), 146.30 (1C,Ar—COH), 152.95 (1C, Ar—COCH₃).

Example 2 Synthesis of2-(hydroxymethyl)-4-methoxy-6-((2-nitro-4-(trifluoro-methyl)-phenyl)diazenyl)-phenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 19.9 g 2-nitro-4-(trifluoromethyl)-aniline (96.5 mmol) (Aldrich,Milwaukee, Wis.), 41 ml concentrated HCl (aq), 100 ml deionized water,100 ml ethanol, and 80 ml THF. The suspension was stirred for 30 minutesand 7.07 g sodium nitrite (102 mmol) in 30 ml water was added dropwiseover 60 minutes while keeping the reaction mixture at 0° C. The reactionmixture was stirred for an additional 1 hour. 300 mg Sulfamic acid wasadded to destroy excess nitrite. The mixture was filtered to removeundissolved solids. The filtered diazonium mixture along with a solutionof sodium hydroxide (15.1 g in 100 ml water) were added dropwise to asolution containing 19.7 g (2-hydroxy-5-methoxy-1,3-phenylene)dimethanol(107 mmol), 4.3 sodium hydroxide, 200 ml deionized water, and 50 ml THFat 0° C. The reaction mixture was allowed to stir at 0° C. for 1 hourand room temperature for 4 hours. The mixture was poured into 3 literswater. The mixture was acidified to pH 3-4. The dark crude product wasfiltered and washed with several liters of water to generate a darksolid which was dried under high vacuum at 55° C. for 72 hours to give15.2 g (42% yield) product.

Synthesis of2-(hydroxymethyl)-4-methoxy-6-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenol

In a 250 ml round bottom flask equipped with a magnetic stirrer wasadded 7.70 g (20.7 mmol)2-(hydroxymethyl)-4-methoxy-6-((2-nitro-4-(trifluoromethyl)phenyl)diazenyl)-phenolfrom Example 2 part 1, 25 ml deionized water, 1.85 g sodium hydroxide,and 80 ml 1-propanol. The mixture was heated to 80° C. and 6.55 g (60.6mmol) formamidine sulfinic acid (Aldrich) was added slowly andconcurrently with a solution of 3.0 g NaOH in 50 ml deionized water. Thereaction mixture was heated at 80° C. for 2 hours. The reaction mixturewas cooled at −20° C. for 2 hours and filtered. The solid was dissolvedin 2.5 L deionized water containing 4 grams NaOH. The pH was adjusted to2.0 using 1 N HCl. The resultant solid was filtered, washed with ampleamounts of deionized water, filtered and dried to give 2.2 g (31%) of ayellow solid. ¹H NMR (CDCl₃) delta: 11.03 (s, 1H, Ar—OH), 8.30 (s, 1H,Ar—H benzotriazole 4-position), 8.07 (d, 1H, Ar—H benzotriazole6-position), 7.88 (s, 1H, Ar—H phenol), 7.69 (d, 1H, Ar—Hbenzotriazole), 7.08 (s, 1H, Ar—H phenol), 4.84 (s, 2H, Ar—CH₂), 3.90(s, 3H, Ar—OCH₃).

Example 3 (Compound WL-1) Synthesis of2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate

In a 250 ml round bottom flask equipped with a magnetic stirrer andnitrogen inlet was dissolved 1.15 g (3.39 mmol)2-(hydroxymethyl)-4-methoxy-6-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenolfrom Example 3 in 50 ml anhydrous THF containing BHT inhibitor(Aldrich). Triethylamine (1.4 ml, 11 mmol) was added and the mixture wascooled to −10° C. Methacryloyl chloride (0.436 g, 4.17 mmol) was addeddropwise and the mixture was stirred for 1 hr at −10° C. followed by 20hours at ambient temperature. The solid was filtered and rinsed with 100ml diethyl ether. The filtrate was poured into 100 ml diethyl ether andwashed with 0.5 N HCl and water. The organic layer was dried withmagnesium sulfate, filtered, and then concentrated via rotaryevaporation to give the desired product as a dark yellow oil which wasrecrystallized in methanol to give 0.35 g product (25%). [M+H⁺]=408.1.¹H NMR (CDCl₃) delta: 10.97 (s, 1H, Ar—OH), 8.30 (s, 1H, Ar—Hbenzotriazole), 8.07 (d, 1H, Ar—H benzotriazole), 7.91 (s, 1H, Ar—Hphenol), 7.69 (d, 1H, Ar—H benzotriazole), 7.10 (s, 1H, Ar—H phenol),6.21 (s, 1H, C═C—H trans), 5.62 (s, 1H, C═C—H cis), 5.40 (s, 2H,Ar—CH₂), 3.90 (s, 3H, Ar—OCH₃), 2.01 (s, 3H, C═C—CH₃). Elementalanalysis: calculated % C (56.02), % H (3.96), % N (10.32), % F (13.99).found % C (56.11), % H (3.96), % N (10.24), % F (14.37).

Example 4 Synthesis of2-((4-fluoro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 25.1 g (161 mmol) 4-fluoro-2-nitroaniline (Aldrich), HCl(aq) (J.T.Baker), 100 ml deionized water, and 100 ml absolute ethanol. Thesuspension was cooled to 0° C. 11.8 g (171 mmol) Sodium nitrite(Sigma-Aldrich) in 50 ml water was added dropwise over 60 minutes whilekeeping the reaction mixture at 0° C. The reaction mixture was stirredfor an additional 1 hour. 420 mg sulfamic acid (Aldrich) was added andthe reaction mixture was stirred for an additional 30 minutes and thenfiltered. In a 1 liter round bottom flask was combined 32.5 g (176 mmol)(2-hydroxy-5-methoxy-1,3-phenylene)dimethanol, 200 ml deionized water,and 200 ml ethanol. 32.3 g (807 mmol) NaOH (Aldrich) was dissolved in100 ml water and approximately one-fourth of this was added to thesolution containing the phenol derivative at 0° C. The diazonium saltsolution and remaining sodium hydroxide solution were added dropwise tothe reaction mixture at 0° C. over a 1 hour period and then allowed tostir for an additional 1 hour at 0° C. and 3 hours at ambienttemperature. The reaction mixture was poured into 3 liters water and thepH was adjusted to 4 using 1N HCl. The solid was collected byfiltration, washed with several liters of water, and vacuum dried (0.1mm Hg) at 55° C. for 72 hours using P₂O₅ as drying agent to afford 29.9g (68%) of a dark solid which was used in the next step without furtherpurification.

Synthesis of2-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxy-methyl)-4-methoxyphenol

In a 500 ml round bottom flask equipped with a magnetic stirrer, liquidaddition funnel, powder addition funnel, and nitrogen inlet was added2-((4-fluoro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenolfrom Example 5 part I and 200 ml ethanol. NaOH (21.7 g, 542 mmol)pellets (97+%, A.C.S. reagent, Aldrich) were dissolved in 100 mldeionized water and approximately one-fourth of the solution was addeddropwise to the reaction mixture. The mixture was subsequently heated to80° C. and 29.3 g (271 mmol) formamidinesulfinic acid (Aldrich) and theremaining sodium hydroxide solution were concurrently added to thereaction mixture over 30 minutes. The mixture was stirred at 80° C. for3 hours and the contents were then poured into 3 L deionized water andacidified to pH 4 using 1N HCl. The solid was collected by filtration,suspended in 300 ml methanol, and stirred for 30 minutes while coolingto below −20° C. The solid was collected by filtration and thensuspended in 300 ml ethanol, cooled again to below −20° C., filtered,and then dried to afford 7.8 g (30%) of a yellow solid, which was usedin the next esterification step.

Example 5 (Compound WL-2) Synthesis of3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate

The esterification was carried out using the product from Example 5. Ina 250 ml round bottom flask equipped with a magnetic stirrer andnitrogen inlet was dissolved 5.06 g (17.5 mmol)2-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenolin 60 ml anhydrous THF. Triethylamine (8.7 ml, 62 mmol)) was added andthe mixture was cooled to −10-0° C. Methacryloyl chloride (2.26 g, 21.6mmol) was added dropwise and the mixture was stirred for 1 hr at −10° C.followed by 20 hours at ambient temperature. The salts were filtered andrinsed with 100 ml THF (≧99.9%, anhydrous containing inhibitor,Aldrich). Diethyl ether (100 ml) was added to the filtrate, which waswashed with 1N HCl and water, dried over magnesium sulfate, filtered,and concentrated by rotary evaporation to give the desired product,which was recrystallized in ethanol to give 2.5 g (40%) of a yellowsolid. ¹H NMR (CDCl₃) delta: 11.03 (s, 1H, phenol OH), 7.94 (m, 1H, Ar—Hbenzotriazole ring), 7.87 (s, 1H, Ar—H phenol ring), 7.53 (m, 1H, Ar—Hbenzotriazole ring), 7.29 (m, 1H, Ar—H benzotriazole ring), 7.05 (s, 1H,Ar—H phenol ring), 6.21 (s, 1H, C═C—H trans), 5.61 (s, 1H, C═C—H cis),5.39 (s, 2H, Ar—CH₂), 3.89 (s, 3H, Ar—OCH₃), 2.01 (s, 3H, C═C—CH₃).

Example 6 Synthesis of2-(hydroxymethyl)-4-methoxy-6-((2-nitrophenyl)-diazenyl)-phenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 19.9 g (144 mmol) 2-nitroaniline (Aldrich), HCl(aq), 100 mldeionized water, and 100 ml EtOH. The mixture was cooled to 0° C. and10.6 g (153 mmol) sodium nitrite in 50 ml water was added dropwise over60 minutes while keeping the reaction mixture between −10-0° C. Thereaction mixture was stirred for an additional 1 hour. 300 mg sulfamicacid was added to destroy excess nitrite and the mixture was stirred foran additional 20 minutes. The solids were filtered and the filtratecontaining the diazonium salt was set aside and kept cold at −10° C.NaOH (29.3 g, 731 mmol) was dissolved in 100 ml water and approximatelyone-fourth was added to a solution of(2-hydroxy-5-methoxy-1,3-phenylene)dimethanol in 100 ml deionized waterand 200 ml ethanol. The diazonium salt mixture and remaining sodiumhydroxide solution were added to the reaction mixture containing thephenol derivative over a 1 hour period at 0° C. The reaction mixture wasallowed to stir at 0° C. for 1 hour and ambient temperature for 3 hours.The contents were poured into 3 liters water and the pH was adjusted to6 using 1N HCl. The resultant solid was washed with several liters ofwater and then dried at 55° C. for 40 hours using P₂O₅ as drying agentto afford 24.4 g (55.8%) of a dark solid which was used in the next stepwithout further purification.

Synthesis of2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol

In a 500 ml round bottom flask equipped with a magnetic stirrer, regularaddition funnel, powder addition funnel, and nitrogen inlet was added23.6 g (77.7 mmol)2-(hydroxymethyl)-4-methoxy-6-((2-nitrophenyl)diazenyl)phenol and 200 mlethanol. NaOH (18.8 g, 470 mmol) was dissolved in 100 ml deionized waterand approximately one-fourth was added dropwise to the reaction mixture.The mixture was heated to 80° C. and 25.1 g (232 mmol) formamidinesulfinic acid and the remaining sodium hydroxide solution wereconcurrently added dropwise to the reaction mixture over 30 minutes. Themixture was stirred at 80° C. for 3 hours, poured into 3.5 L water, andthen acidified to pH 4 using 1 N HCl. The resultant solid was collectedby filtration and worked up as in Example 5 to give a light yellow solid(4.3 g, 20.5%).

Example 7 (Compound WL-3) Synthesis of3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate

In a 250 ml round bottom flask equipped with a magnetic stirrer andnitrogen inlet was dissolved 4.03 g (14.9 mmol)2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenolfrom Example 7 in 50 ml anhydrous THF. Triethylamine (7.4 ml, 53 mmol)was added and the mixture was cooled to −10° C. Methacryloyl chloride(1.99 g, 19.0 mmol) was added dropwise and the mixture was stirred for 1hr at 0° C. followed by 6 hours at ambient temperature. The mixture waspoured into 200 ml diethyl ether and washed with 0.5 N HCl and water.The organic layer was dried with magnesium sulfate, filtered, andconcentrated via rotary evaporation to give the desired product as adark yellow oil which was recrystallized in methanol to give 1.73 g of alight yellow solid (34%). ¹H NMR (CDCl₃) delta: 11.26 (s, 1H, Ar—OH),7.92 (d, 2H, Ar—H benzotriazole), 7.91 (s, 1H, Ar—H meta to phenol),7.49 (d, 2H, Ar—H benzotriazole, 5,6-position), 7.05 (s, 1H, Ar—H metato phenol), 6.21 (s, 1H, C═C—H trans), 5.61 (s, 1H, C═C—H cis), 5.40 (s,2H, Ar—CH₂), 3.90 (s, 3H, Ar—OCH₃), 2.01 (s, 3H, C═C—CH₃).

Example 8 Synthesis of2-((5-chloro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 30.0 g (174 mmol) 5-chloro-2-nitroaniline (Aldrich), conc. HCl(aq)(J.T. Baker), 100 ml deionized water and 100 ml absolute ethanol. Thesuspension was cooled to 0° C. and 12.7 g (184 mmol) sodium nitrite in50 ml water was added, dropwise over 30 minutes while keeping thereaction mixture at 0° C. The reaction mixture was stirred for anadditional 1 hour. Sulfamic acid (430 mg) was added to destroy excessnitrite and the reaction mixture was stirred for an additional 20minutes. The solids were filtered and the filtrate containing thediazonium salt was set aside and kept cold at −10° C. NaOH (34.9 g, 873mmol) was dissolved in 100 ml water and approximately one-fourth wasadded to a solution of (2-hydroxy-5-methoxy-1,3-phenylene)dimethanol in100 ml deionized water and 200 ml ethanol. The diazonium salt mixtureand remaining sodium hydroxide solution were added to the reactionmixture containing the phenol derivative over a 1 hour period at 0° C.The reaction mixture was allowed to stir at 0° C. for 1 hour and ambienttemperature for 2 hours. The contents were poured into 3 liters waterand the pH was adjusted to 5 using 1N HCl. The resultant solid waswashed with several liters of water and then vacuum dried (0.1 mm Hg) at55° C. for 40 hours using P₂O₅ as drying agent to afford 28.0 g (48%) ofa dark solid which was used in the next step without furtherpurification.

Synthesis of2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxy-methyl)-4-methoxyphenol

In a 500 ml round bottom flask equipped with a magnetic stirrer,addition funnel, powder addition funnel, and nitrogen inlet was added27.4 g (81.0 mmol)2-((5-chloro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenoland 200 ml ethanol. NaOH (19.7 g, 493 mmol) was dissolved in 100 mldeionized water and approximately one-fourth was added dropwise to thereaction mixture. The mixture was heated to 80° C. and 26.5 g (245 mmol)formamidine sulfinic acid and the remaining sodium hydroxide solutionwere concurrently added dropwise to the reaction mixture. The mixturewas stirred at 80° C. for 2 hours and then poured into 3 L deionizedwater. The mixture was acidified to pH 3 using 1N HCl and the solid wascollected by filtration, rinsed with ample amounts of water, and thenworked up as in Example 5 to afford 7.4 g (30%) solid which was used inthe next esterification step.

Example 9 (Compound WL-4) Synthesis of3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate

In a 250 ml round bottom flask equipped with a magnetic stirrer andnitrogen inlet was dissolved 3.98 g (13.0 mmol)2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenolin 60 ml anhydrous THF. Triethylamine (6.4 ml) was added and the mixturewas cooled to −10-0° C. Methacryloyl chloride (1.62 g, 15.5 mmol) wasadded dropwise and the mixture was stirred for 1 hr at −10-0° C.followed by 20 hours at ambient temperature. The solid was filtered andrinsed with 100 ml diethyl ether. The organic layer was washed with 1 NHCl and water, dried with magnesium sulfate, filtered, and concentratedvia rotary evaporation to yield a yellow oil which was recrystallized inethanol to give 1.73 g (34%) of a light yellow solid. ¹H NMR (CDCl₃)delta: 11.00 (s, 1H, Ar—OH), 7.92 (s, 1H, Ar—H benzotriazole), 7.88 (s,1H, Ar—H phenol), 7.87 (d, 1H, Ar—H benzotriazole), 7.45 (d, 1H, Ar—Hbenzotriazole), 7.06 (s, 1H, Ar—H phenol), 6.21 (s, 1H, C═C—H trans),5.62 (s, 1H, C═C—H cis), 5.38 (s, 2H, Ar—CH₂), 3.89 (s, 3H, Ar—OCH₃),2.01 (s, 3H, C═C—CH₃).

Example 10 Synthesis of2-(2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 24.8 g (148 mmol) 4-methoxy-2-nitroaniline (Aldrich), conc.HCl(aq) (J.T. Baker), 150 ml water, and 150 ml absolute ethanol. Themixture was cooled to −20° C. and a solution comprised of 10.8 (156mmol) sodium nitrite in 40 ml water was added dropwise over 30 minutes.The reaction mixture was stirred for an additional 1 hour and thensulfamic acid (315 mg) was added to destroy excess nitrite. Theundissolved solids were filtered and the filtrate containing thediazonium salt was set aside and kept cold at −10° C. NaOH (29.5 g, 739mmol) was dissolved in 100 ml water and approximately one-fourth wasadded to a solution comprised of(2-hydroxy-5-methoxy-1,3-phenylene)dimethanol in 100 ml deionized waterand 200 ml ethanol. The diazonium salt mixture and remaining sodiumhydroxide solution were added to the reaction mixture containing thephenol derivative over a 1 hour period at 0° C. The reaction mixture wasallowed to stir at 0° C. for 1 hour and ambient temperature for 3 hours.The contents were poured into 3 liters water and the pH was adjusted to4.5 using 1N HCl. The resultant solid was filtered, washed with severalliters of water, and then vacuum dried (0.1 mm Hg) at 65° C. for 20hours using P₂O₅ as drying agent to afford 33.5 g (68%) of a dark solidwhich was used in the next step without further purification.

Synthesis of2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenol

In a 500 ml round bottom 3-neck flask equipped with a magnetic stirrer,addition funnel, powder addition funnel, and nitrogen inlet was added2-(hydroxymethyl)-4-methoxy-6-((4-methoxy-2-nitrophenyl)diazenyl)phenolfrom Example 11 and 200 ml absolute ethanol (Pharmco Products,Brookfield, Conn.). NaOH pellets, 97% (Aldrich, 16.8 g, 420 mmol) weredissolved in 80 ml deionized water and approximately one-fourth of thesolution was added dropwise to the azo mixture. The reaction mixture washeated to 80° C. and 22.6 g (209 mmol) formamidinesulfinic acid(Aldrich) and the remaining NaOH solution were added concurrently to theazo mixture over 0.5 hr. The mixture was heated at 80° C. for 3 hours,poured into 3.5 L water, and acidified to pH 4-5 with conc. HCl (J.T.Baker). The crude product was recrystallised from ethanol and thencollected and vacuum dried (0.1 mm Hg) at 50° C. for 72 hours to give 7g (27%) of a light yellow solid.

Example 11 (Compound WL-5) Synthesis of2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate

The esterification was carried out using the product from Example 11. Ina 100 ml round bottom 3-neck flask equipped with a magnetic stirrer andnitrogen inlet was dissolved 3.24 g (10.8 mmol)2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenolin 60 ml anhydrous THF. Triethylamine (1.2 ml) was added and the mixturewas cooled to −10-0° C. Methacryloyl chloride (1.40 g, 13.4 mmol) wasadded dropwise and the mixture was stirred for 2 hr at 0° C. followed by20 hours at ambient temperature. The salts were filtered off and thefiltrate was poured into 100 ml diethyl ether and washed with 0.5 N HCland water. The organic layer was dried with magnesium sulfate, filtered,and concentrated via rotary evaporation to give the desired product as adark yellow oil which was recrystallized in ethanol to give a lightyellow solid. ¹H NMR (CDCl₃) delta: 11.20 (s, 1H, phenol OH), 7.80 (m,1H, Ar—H benzotriazole), 7.77 (s, 1H, Ar—H phenol), 7.17 (m, 1H, Ar—Hbenzotriazole), 7.14 (s, 1H, Ar—H phenol), 7.10 (m, 1H, Ar—Hbenzotriazole), to 6.21 (s, 1H, C═C—H trans), 5.61 (s, 1H, C═C—H cis),5.38 (s, 2H, Ar—CH₂), 3.92 (s, 3H, Ar—OCH₃, phenol), 3.88 (s, 3H,Ar—OCH₃, benzotriazole), 2.01 (s, 3H, C═C—CH₃).

Example 12 Synthesis of2-(hydroxymethyl)-4-methoxy-6-((4-methyl-2-nitrophenyl)-diazenyl)phenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wasadded 24.3 g (160 mmol) 4-methyl-2-nitroaniline, 98% (Aldrich), 67 mlconc. HCl(aq), 100 ml water, and 100 ml absolute ethanol. The mixturewas cooled to −10-0° C. and 11.6 g (169 mmol) sodium nitrite in 40 mlwater was added dropwise over 30 minutes at −10-0° C. The reactionmixture was stirred for an additional 1 hour and 315 mg sulfamic acidwas added to destroy excess nitrite. After an additional 20 minutes ofstirring the reaction mixture was filtered and the cold filtrate was setaside. In a 1 L flask was suspended(2-hydroxy-5-methoxy-1,3-phenylene)dimethanol in 200 ml deionized waterand 100 ml ethanol. A solution of 32.2 g (805 mmol) sodium hydroxide wasprepared and approximately one-fourth was added to the phenolderivative. The phenol derivative was cooled to 0° C. and the diazoniumsalt mixture and remaining sodium hydroxide solution were addedconcurrently to the phenol derivative over 1 hour at 0° C. The reactionmixture was stirred at 0° C. for 1 hour and ambient temperature for 3hours. The mixture was poured into 3 liters water and the pH wasadjusted to 4.5 using 1N HCl. The crude product was dried at 65° C. for20 hours under high vacuum (0.1 mm Hg) using P₂O₅ as drying agent toafford 30.8 g (61%). The product was used in the next step withoutfurther purification.

Synthesis of2-(hydroxymethyl)-4-methoxy-6-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)phenol

In a 500 ml round bottom 3-neck flask equipped with a magnetic stirrer,regular addition funnel, powder addition funnel, and nitrogen inlet wasadded 30.0 g (94.6 mmol) of the azo compound from part 1 and 200 mlethanol. NaOH (22.9 g, 573 mmol) was dissolved in 100 ml deionized waterand approximately one-fourth of the solution was added dropwise to thereaction mixture. The reaction mixture was heated to 80° C.Formamidinesulfinic acid (30.7 g, 284 mmol) and the remaining sodiumhydroxide solution were added concurrently to the azo mixture over 30minutes. The mixture was heated at 80° C. for 3 hours. The reactionmixture was poured into 3 L water and then acidified to pH 4-5 with 1NHCl. The solid was filtered and then dissolved in 3 L water containing 5grams NaOH and acidified to pH 2 with 1N HCl. The solid was filteredagain and then dried at 55° C. under high vacuum (0.1 mm Hg) for 40hours to afford 20 g (74%) which was used in the next step withoutfurther purification.

Example 13 (Compound WL-6) Synthesis of2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate

In a 100 ml round bottom 3-neck flask equipped with a magnetic stirrerand nitrogen inlet was dissolved 19.5 g (68.3 mmol)2-(hydroxymethyl)-4-methoxy-6-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)phenolin 200 ml anhydrous THF. Triethylamine (34 ml, 240 mmol) was added andthe mixture was cooled to −10° C. Methacryloyl chloride (8.55 g, 81.8mmol) was added dropwise and the mixture was stirred for 2 hr at 0° C.followed by 20 hours at ambient temperature. The solid was filtered andrinsed with diethyl ether and the filtrate was poured into 100 mldiethyl ether and washed with 0.5 N HCl and water. The organic layer wasdried with magnesium sulfate, filtered, and concentrated via rotaryevaporation. The crude product was recrystallized in ethanol to give 7.2g (30%) of a light yellow solid. ¹H NMR (CDCl₃) delta: 11.28 (s, 1H,Ar—OH), 7.89 (s, 1H, Ar—H benzotriazole 4-position), 7.79 (d, 1H, Ar—Hbenzotriazole 6-position), 7.66 (s, 1H, Ar—H phenol 6-position), 7.26(d, 1H, Ar—H benzotriazole 7-position), 7.03 (s, 1H, Ar—H phenol4-position), 6.21 (s, 1H, C═C—H trans), 5.61 (s, 1H, C═C—H cis), 5.39(s, 2H, Ar—CH₂), 3.89 (s, 3H, Ar—OCH₃), 2.54 (s, 3H, Ar—CH₃), 2.01 (s,3H, C═C—CH₃).

Example 14 Synthesis of2-(hydroxymethyl)-4-methyl-6-((2-nitro-4-(trifluoromethyl)-phenyl)-diazenyl)phenol

In a 500 ml round bottom flask equipped with a magnetic stirrer wascombined 26.0 g (126 mmol) 2-nitro-4-(trifluoromethyl)-aniline, 5.3 mlconc. HCl, 100 ml deionized water, and 150 ml ethanol. The mixture wascooled to 0° C. and sodium nitrite in 30 ml water was added dropwiseover 60 minutes. The reaction mixture was stirred for an additional 1hour and 300 mg sulfamic acid was added to destroy the excess nitrite.The solids were filtered and the cold filtrate was set aside. In a 1liter flask was suspended (2-hydroxy-5-methoxy-1,3-phenylene)dimethanolin 200 ml deionized water and 100 ml ethanol. Approximately one-fourthof a solution of sodium hydroxide (25.4 g, 635 mmol) in 100 ml water wasadded to the phenolic mixture at 0° C. The diazonium salt mixture andremaining sodium hydroxide solution were added concurrently to thephenolic mixture over 1 hour. The reaction mixture was allowed to stirat 0° C. for 1 hour and room temperature for 4 hours. The mixture waspoured in 3 liters water and the pH adjusted to 3-4 using 1N HCl. Thesolid was filtered and washed with ample amounts of water and thenvacuum dried (0.1 mm Hg) at 55° C. for 40 hours to give 27.4 g (76%) ofa red solid.

Synthesis of2-(hydroxymethyl)-4-methyl-6-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenol

In a 1 L round bottom flask equipped with a magnetic stirrer, additionfunnel, powder addition funnel, and nitrogen inlet was added 26.0 g(73.2 mmol)2-(hydroxymethyl)-4-methyl-6-((2-nitro-4-(trifluoromethyl)phenyl)-diazenyl)phenoland 300 ml ethanol. Sodium hydroxide (17.6 g, 441 mmol) was dissolved in100 ml deionized water and approximately one fourth was added dropwiseto the azo mixture. The reaction mixture was heated to 80° C. and 23.9 g(221 mmol) formamidinesulfinic acid and the remaining sodium hydroxidesolution were added to the azo mixture over 30 minutes. The reactionmixture was heated at 80° C. for 3 hours, poured in 3 L deionized water,and acidified to pH 4 using 1N HCl. The solid was collected by vacuumfiltration, washed with ample amounts of water, and then dried for 20hours under vacuum (0.1 mm Hg) at 42° C. to give 18.6 g (79%) of an offwhite solid.

Example 15 (Compound WL-7) Synthesis of2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate

In a 100 ml round bottom 3-neck flask equipped with a magnetic stirrerand nitrogen inlet was dissolved 3.58 g (11.1 mmol)2-(hydroxymethyl)-4-methyl-6-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenolin 60 ml anhydrous THF. Triethylamine (5.6 ml, 40 mmol) was added andthe mixture was cooled to −10° C. Methacryloyl chloride (1.373 g, 13.1mmol) was added dropwise and the mixture was stirred for 1 hour at −10°C. followed by 20 hours at ambient temperature. The solid was filteredoff and rinsed with diethyl ether and the resultant filtrate was pouredinto 100 ml diethyl ether and washed with 0.5 N HCl and water. Theorganic layer was dried with magnesium sulfate, filtered, andrecrystallized with diethyl ether to give 1.90 g (44%) of a white solid.¹H NMR (CDCl₃) delta: 11.17 (s, 1H, Ar—OH), 8.29 (s, 1H, Ar—Hbenzotriazole 4-position), 8.21 (s, 1H, Ar—H phenol 6-position), 8.06(d, 1H, Ar—H benzotriazole 6-position), 7.69 (d, 1H, Ar—H benzotriazole7-position), 7.29 (s, 1H, Ar—H phenol 4-position), 6.20 (s, 1H, C═C—Htrans), 5.61 (s, 1H, C═C—H cis), 5.39 (s, 2H, Ar—CH₂), 2.42 (s, 3H,Ar—CH₃), 2.00 (s, 3H, C═C—CH₃).

Example 16

Transmittance curves for Compounds WL-1 through WL-7 were generated byUV/Vis spectroscopy. Each compound was dissolved in chloroform andevaluated in a PerkinElmer Lambda 35 UV/Vis spectrometer. The resultsare shown in FIG. 1 and the 1% T and 10% T results are shown in Table 1.

TABLE 1 Concen- Concen- 1% T 10% T tration tration wavelength wavelengthCompound (mM) (w/v %) (nm) (nm) WL-1 4.12 0.168 428 433 WL-2 4.14 0.148416 421 WL-3 4.10 0.139 413 418 WL-4 4.15 0.155 423 428 WL-5 4.06 0.150411 416 WL-6 4.24 0.150 411 416 WL-7 4.22 0.165 399 403

Example 17 Acrylic IOL Formulations

Compounds WL-1-WL-4 were formulated in IOL materials as shown in Tables2-6. All components were vortex mixed in a 30 ml glass vial, degassedwith nitrogen, and then syringe filtered using a 0.2 micron Teflonfilter into ˜1 mm deep rectangular polypropylene molds. Samples werethermally cured at 70° C. for 1 hour and 110° C. for 2 hours and thenextracted in acetone at 50° C. for 6 hours with fresh solventreplacement every 90 minutes.

TABLE 2 Example (% w/w) Component 17A 17B Compound WL-1 1.81 1.81(Example 3) N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)-ethylmethylacrylamide PEA 48.8 — PEMA 42.9 — BzA — 79.7 BzMA — 12.0Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester BDDA 1.501.51 AIBN 0.56 0.59 PEA = 2-phenylethyl acrylate PEMA = 2-phenylethylmethacrylate BzA = benzyl acrylate BzMA = benzyl methacrylate BDDA =1,4-butanediol diacrylate Secondary alcohol ethoxylate, methacrylic acidester = methacrylic acid ester of Tergitol ™ 15-S-30 surfactant(Dow/Union Carbide) AIBN = 2,2′-Azobis(2-methylpropionitrile)

TABLE 3 Example (% w/w) Component 17C 17D Compound WL-2 1.81 1.81(Example 5) N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)-ethylmethylacrylamide PEA 48.8 — PEMA 42.9 — BzA — 79.7 BzMA — 12.0Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester BDDA 1.501.51 AIBN 0.55 0.53

TABLE 4 Example (% w/w) Component 17E 17F Compound WL-3 1.80 1.82(Example 7) N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)-ethylmethylacrylamide PEA 48.8 — PEMA 42.9 — BzA — 79.7 BzMA — 12.0Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester BDDA 1.501.51 AIBN 0.50 0.52

TABLE 5 Example (% w/w) Component 17G 17H Compound WL-4 1.80 1.80(Example 9) N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)-ethylmethylacrylamide PEA 48.8 — PEMA 42.9 — BzA — 79.7 BzMA — 12.0Secondary alcohol 5.00 5.00 ethoxylate, methacrylic acid ester BDDA 1.501.50 AIBN 0.50 0.51

TABLE 6 Example (% w/w) Component 17I 17J Compound WL-1 1.67 — (Example3) Compound WL-4 — 1.53 (Example 9) BzA 83.7 83.9 BzMA 10.0 10.0PolyPEGMA 3.02 3.03 BDDA 1.58 1.53 AIBN 0.50 0.51 PolyPEGMA =Macromonomer of poly(ethylene glycol) monomethyl ether methacrylate (MW= 550), Mn (SEC): 4100 Daltons, Mn (NMR): 3200 Daltons, PDI = 1.50.

Example 18 Photostability

Samples of Formulations 17A, 17B, 17C, 17D, 17E, 17F, 17G, 17H, 17I, and17J were subject to UV radiation from 300 to 800 nm using an AtlasSuntest CPS+ test chamber (Atlas Electric Devices Company, Chicago,Ill.) utilizing a xenon arc lamp with light intensity of approximately8-10 mW/cm² at the height of the test sample. The temperature of the PBSmedium was 35° C. UV/Vis spectra from 0.9 mm thick sample sections werecollected using a PerkinElmer Lambda 35 UV/Vis spectrometer. Resultsfrom light exposure equivalent to 20 years (Examples 17A-17H) or 10years (Examples 17I and 17J) are shown in FIGS. 2A-2J.

This invention has been described by reference to certain preferredembodiments; however, it should be understood that it may be embodied inother specific forms or variations thereof without departing from itsspecial or essential characteristics. The embodiments described aboveare therefore considered to be illustrative in all respects and notrestrictive, the scope of the invention being indicated by the appendedclaims rather than by the foregoing description.

1. An intraocular or contact lens comprising an ophthalmic devicematerial formed by copolymerizing a composition comprising i) adevice-forming monomer selected from the group consisting of acrylicmonomers and silicone-containing monomers, and ii) a benzotriazolecompound of the formula

wherein R¹=H, CH₃, CH₂CH₃, or CH₂OH; R²=C₁-C₄ alkyl; and R³=H, CH₃,CH₃O, F, Cl, Br, I, or CF₃.
 2. The lens of claim 1 wherein R¹=H or CH₃;R²=C₁-C₄ alkyl; and R³=H, CH₃, CH₃O, F, Cl, or CF₃.
 3. The lens of claim1 wherein the benzotriazole compound is2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate.
 4. The lens of claim 1 wherein the ophthalmic devicematerial comprises from 0.1 to 3% w/w of the benzotriazole compound. 5.The lens of claim 4 wherein the ophthalmic device material comprisesfrom 0.2 to 2.5% w/w of the benzotriazole compound.
 6. The lens of claim5 wherein the ophthalmic device material comprises from 0.3 to 2% w/w ofthe benzotriazole compound.
 7. The lens of claim 1 wherein theophthalmic device material comprises a device-forming monomer of formula[IV]:

where in formula [IV]: A is H, CH₃, CH₂CH₃, or CH₂OH; B is (CH₂)_(m) or[O(CH₂)₂]_(z); C is (CH₂)_(w); m is 2-6; z is 1-10; Y is nothing, O, S,or NR′, provided that if Y is O, S, or NR′, then B is (CH₂)_(m); R′ isH, CH₃, C_(n′)H_(2n′+1), iso-OC₃H₇, C₆H₅, or CH₂C₆H₅; n′ is 1-10; w is0-6, provided that m+w≦8; and D is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₆H₅,CH₂C₆H₅, or halogen.
 8. The lens of claim 7 wherein in formula [IV]: Ais H or CH₃; B is (CH₂)_(m); m is 2-5; Y is nothing or O; w is 0-1; andD is H.
 9. The lens of claim 8 wherein the ophthalmic device materialcomprises a monomer selected from the group consisting of: 2-phenylethylmethacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate;2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate; andtheir corresponding acrylates.
 10. The lens of claim 1 wherein theophthalmic device material comprises a cross-linking agent.
 11. The lensof claim 1 wherein the ophthalmic device material comprises a reactiveblue-light absorbing compound.